CN1303004C - Method of electrolytic treatment of industrial or aquaculture waste water - Google Patents
Method of electrolytic treatment of industrial or aquaculture waste water Download PDFInfo
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Abstract
The invention relates to a method of removing organic pollutant, ammonia-nitrogen, coloring matter, over-propagated alga and phytoplankton via breaking, chemical reaction, effective oxidation or floatation actions by electrolytic treatment, and performing a disinfection action. The invention also relates to a waste water cleaning device.
Description
Technical field
The present invention relates to electrolysis by breaking, chemical reaction, and the algae and the plant plankton of organic pollution materials in industry or the aquiculture waste water, ammonia nitrogen, pigment, excessive multiplication are removed in oxidation or flotation effect, and can play the method for disinfection.The invention still further relates to a cover effluent treatment plant.
Background technology
Biological removal of nitrogen is difficult to deep-well bittern and handles, and this is that iodine is not only toxic to microorganism, and special salt is arranged because still contain a small amount of remaining iodine in the water after handling.Studies show that with biological process and from salt solution, denitrogenate than from fresh water, denitrogenating slow several hrs.The laboratory early-stage Study result of Catalan-Sakairin (1996) shows that the best nitrogen portative power of immobilization biological nitrogenize/denitrogenation treatment system in salt solution is than low 6 times in fresh water.And the biological removal of nitrogen method needs a kind of organic compound as electron donor, thereby has increased processing costs.
Tanaka etc. (2002) be though report can effectively be removed ammonia in the seawater with the ozonize method,, ozone is made the practical application that this unfavorable factor of cost height has limited this method.
Migo etc. (1993,1997) report can be removed pigment in the biological degradation waste water with the polycation flocculation agent.The result shows its decolorizing efficiency greater than 90%, and total organic carbon (TOC) is removed efficient greater than 70%.Though pigment can be removed fully, produced a large amount of mud shape refuses, this has brought the secondary pollution problem again.
Alfafara etc. (2000) report ozonize also can be used for removing pigment from the molasses factory effluent.Though this method decolorizing efficiency is up to 80%,, it is but very low that organism is removed efficient (being COD), and the treatment time reaches 40 hours.
Though, can from the lake water of nutrition accumulationization, remove algae with chemical flocculation by precipitation, centrifugal, traditional electric electric floating effect of floating method (as DAF) or dissolved air,, the fund input aspect the chemical floc or the energy is bigger.
Owing to have many problems in the above-mentioned effluent purification method, so electrolytic process receives much attention.Treatment with electrolytic method helps to remove the algae and the plant plankton of organic pollutant, ammonia nitrogen, pigment, excessive breeding from industry and aquiculture waste water, and has disinfection.
Another advantage of the present invention has provided one more effectively and avoided the processing method of all drawbacks in the prior art.
An advantage more of the present invention has provided the device of implementing treatment process of the present invention.
Description of drawings
Fig. 1 is the device schema of operation the inventive method in the laboratory.
Fig. 2 is the sectional view of squirt pump.
Fig. 3 is the flow velocity schema of pending liquid or waste water.
Fig. 4 is the synoptic diagram that is applied to the liquid circulation model in the industrial sewage treating pond of the pond of aquaculture or close scale or lakelet or marsh.
Fig. 5 is the schematic layout pattern in the water treatment system in the industrial sewage treating pond of typical aquaculture pond or close scale or lakelet or marsh.
Fig. 6 is the synoptic diagram that is applied to the density flow general formula treatment system in bigger lake and marsh.
Fig. 7 has shown that in electrolytic process the variation of water pollutant (organic content and pigment) concentration is flowed out in the distillation during trade effluent and molasses are produced after the anaerobic digestion.Organic content represents that with COD pigment is represented with the photoabsorption at 465nm.
Fig. 8 has shown that electrolytic process is handled trade effluent and change in color in the waste water process is distilled in molasses production.
Fig. 9 has shown that the time course of removing ammonia from deep-well bittern changes.Figure 10 has shown that the time course of in electrolytic acid cleaning oxydation process ammonia and COD in the landfill refuse leachate being removed changes.
Figure 11 is the schematic diagram that electric floating method is removed algae.
Figure 12 has shown that carrying out the time course that algae is removed under different input electric power conditions in the electric floating treating processes at the lake water to nutrition accumulation changes (algae concentration is represented with chlorophyll concentration).Electrolytic condition is average 50 volts, and electric current is to draw divided by voltage by the power with input.
Detailed description of the present invention
Advantage of the present invention will be embodied in purified industrial or the aquiculture waste water.Electrolytic action is to realize by an electrolytic module that is coupled to or integrated on the liquid circulation module.Electrolytic module is made up of a plurality of parallel negative electrode and the positive plate that link to each other with power supply.Wherein liquid circulation module comprises a cylindrical tubes with inlet end and exit end, and this cylindrical tubes has also comprised one and driven in liquid unit.Battery lead plate is enclosed in the cylindrical tubes of liquid circulation module and is fixed on and drives in unitary upstream section.Treatment step comprises the inlet end that waste water to be processed is incorporated into the liquid circulation module, then with the direction parallel electrolytic module of flowing through with battery lead plate, by producing electric current to the electrode pressurization, come oxidation or the floating pollutent of removing the waste water stream of electricity so that discharge ion from anode, thereby purify waste water according to this, preferably treated water is discharged from exit end.
According to the present invention, sintering platinum or polyvalent metal alloy system positive plate are than aluminium or iron positive plate better effects if.
According to another characteristics of the present invention, it is better than stainless steel or titanium alloys negative electrode not produce metals deposited alloy system negative electrode.
Characteristics more of the present invention are that liquid drives in the unit and comprised a squirt pump or density flow producer.
Another advantage also comprises this wastewater treatment equipment, and described device comprises the electrolytic module that is coupled to or integrated on the liquid circulation module.Electrolytic module is made up of a plurality of parallel negative electrode and the positive plate that link to each other with voltage source.Wherein liquid circulation module comprises a cylindrical tubes with inlet end and exit end, and it comprises one and drives in liquid unit.Battery lead plate is enclosed in the cylindrical tubes of liquid circulation module and is fixed on and drives in unitary upstream section.
Based on effective mixing of electrochemistry generation and oxygenant, a purification method for effluent is succeeded in developing.This flow process can be applicable to remove the algae and the plant plankton of organic pollutant in industry and the aquiculture waste water (for example BOD, COD or TOC), ammonia nitrogen, color, excessive breeding, and has disinfection.This system comprises an electrolytic module (Fig. 1) that is coupled to or integrated on the liquid circulation module.
Electrolytic module is made up of the parallel battery lead plate 1 that is connected on the voltage source 2.The compound that electrolytic module produces assists to remove or destroy target contaminant by physics or chemical reaction.The compound that these electrochemical reactions produced and the mechanism of removing of target contaminant depend on the type of electrode and the character of used liquid.In wastewater treatment process of the present invention, its mechanism of action may be summarized to be " electricity is floating " or " electrooxidation ".In electric flotation process, electrode produces floating effect and agglutinating matter, thereby can be used for removing suspended solids, the bioseston (as algae) that maybe will remove as gluey soil particle.In electro-oxidation process, destroy target contaminant by redoxomorphism thereby on electrode, produce oxygenant.Because the oxidizing substance that produces on electrode is based on chlorine, so better to the treatment effect of the waste water of brine waste or chloride ion-containing.This effect can be used for removing and resembles BOD or COD, ammonia, obstinate organic pollutants such as organic compound, and depigmentation or to the sterilization of cause of disease.Based on the type of electrode used therein, the electrochemical reaction product may be flocculation agent, the leafing agent resemble hydrogen resemble aluminium hydroxide or resemble such oxygenant of hypochlorous acid, hypobromous acid etc.Battery lead plate 1 is wrapped in the cylindrical tubes 3 of liquid circulation module 4, and is fixed on the upstream section that drives in liquid unit 5, and this will partly be described in detail below.
Basic liquid circulation module 4 comprises that one comprises the cylindrical tubes 3 that drives in liquid unit 5, and water can flow to exit end from the inlet end of cylindrical tubes.Drive in liquid unit 5 and partly or entirely can be used as liquid in the suction of inlet end and the discharge of exit end.Fluidic sucks and discharges the liquid unit 5 that drives in that can be made up of squirt pump 6 or density flow producer 7 and drives.
Squirt pump 6 (Fig. 2) is fixed and is wrapped in the cylindric outer tube 3 by metal insert 8, and has the interior pipe of a slit.It utilizes the principle of jet displacer that liquid is effectively mixed or recirculation (Fig. 3).A pipe connecting 10 drives liquid by the slit in the squirt pump to the water pump 9 on the squirt pump 6 with flow velocity Q1.Liquid provides a pressure to fall as the power that drives liquid suction outer tube from the discharge (flow velocity is Q1+Q2) of slit and interior pipe.From the final discharge flow velocity of outer tube become bigger (Q1+Q2+Q3).Because pipe and outer tube in draining occurs in, can be regarded as two-stage based on the fluid circulation system of squirt pump and discharge system or dual discharge system.
In case injection stream is set up, and will produce an intense mixing district at the outlet end near zone.Liquid around the injection stream also is involved in the liquid stream.Consequently more liquid is involved in injection stream, and this liquid stream will promote the mixing of liquid.Therefore, it is optimal that electrolytic module is installed in upstream section, and the electrochemical reaction product will effectively be mixed in the intense mixing district with target contaminant like this.There is very short distance in the intense mixing district from jet exit usually.This characteristic makes pollutent and electrochemical reaction product effecting reaction.Therefore, injection stream has become the liquid stream of handling.
Brought other advantage to treatment with electrolytic method again with spraying cycle is module integrated to electrolytic module, this can not produce in the unit electrolysis wastewater is handled.From the chemical engineering angle, the violent shearing force that produces by squirt pump make the electrochemical reaction product with high coefficient of mass transfer to Liquid Phase Diffusion, promote the reaction with target contaminant, and avoided the stained of counter electrode.Electrode is stained to derive from calcium salt or the magnesium salts deposition at cathode surface.At negative electrode, oxyhydroxide alkalescence is primary product.Intensive shearing force and effective mixing effect have avoided the pH value of cathode surface locality to change, thereby have also avoided the deposition of this compounds.
This system can be as independently unit use (Fig. 2) in included reactor.For handling shallow (about 1 meter to 2 meters) and medium scale treating pond or pond (about 10,000 square metres), this processing unit is compact and be convenient to transport.Also can comprise a floatation device 11, liquor pump 12 and an engine (13) (Fig. 4).
When handling big area or very dark water body, owing to need very strong mixing ability, so will use the liquid unit that drives in that can produce mixing zone on a large scale.For the liquid circulation of very big or profound water body, density flow producer 7 more suitable (Fig. 6).Density flow producer 7 sucks low density water and sucks higher density water simultaneously from the bottom from the surface, and ejection enters the middle layer after using a thruster (14) that water is mixed.This intermediate density mixing water can produce a kind of density flow that can cause long apart from horizontal proliferation.Density flow is meant that the liquid of a certain density that flows into another different densities liquid layer will flow to the phenomenon of isopycnic liquid layer with it, if there are the successive current to replenish behind this density flow, it will follow the quite long distance of this water layer stream.In the density flow producer, electrolytic module is installed in the upstream section of fluid circulation system.
The water treatment system be made of using on the spot of electrolysis process comprises open tank, treating pond, aquaculture pond or large-area lake and marsh applicable to water body environment widely.It also is applicable to the reactor assembly of low capacity.Though it still has other potential purposes, its major objective is to improve the quality of all kinds of water, and also plays the effect of environment purification.
Electrolysis treatment both can be the electrooxidation effect, also can be electric floating effect.Can be removed by this water purification system or the neutral principal pollutant comprise solid and other pollutent of organism, ammonia, pathogenic agent, algae, suspension.
Inactive anode of electrochemical properties and negative electrode have been used in the electrooxidation effect.Exist under the chlorion condition, producing oxidizer containing chlorine, and producing bubble hydrogen at negative electrode at anode.Electrooxidation is applicable to from trade effluent or aquaculture water removes pollutent, for example comprises organism, ammonia nitrogen, nitrite nitrogen, the hydrogen sulfide of BOD, COD or TOC, algae and the plant plankton and the pigment of excessive breeding.It also is applicable to the sterilization to pathogenic micro-organism.
The floating effect of electricity mainly is applicable to the solid of removing suspension, also obtains utilizing as second-order effect sometimes, and it also can remove some BOD or COD in anhydrating.The active anode of electrochemical properties contains polyvalent metal, can be used for producing flocculation agent (flocculation agent may be the mixture by electrochemical reaction dissolved aluminium or iron ion, or its corresponding oxyhydroxide) as aluminium alloy or iron alloy and assemble fine suspended particle (being turbidity).These flosss maybe can be removed by sedimentation in the later step, or can (if they are enough light) floating by the leafing agent (normally little bubble hydrogen) that produces at negative electrode.
The present invention further illustrates by following unrestricted (non-limiting) example.
The electrooxidation example:
Example I utilizes after the electrooxidation method anaerobic treatment alcohol wastewater that contains from molasses production ethanol process to remove COD and pigment.
To contain the alcoholic acid molasses with artificial seawater and produce alcoholic acid waste water by 50 to 50 dilution proportion.Derive from about 3.9 amperes of the initial operation electric current of variable power supply.In order effectively to mix and to produce maximum liquid shear power stained to prevent electrode, agglomerating platinum anode and titanium alloy negative electrode are connected in position near minisize liquid circulation module.Fig. 7 has shown that the time course of COD and pigment changes.As shown in the figure, up to 169,000mg/L is dark-brown sewage for the COD starting point concentration, and treatment with electrolytic method can be removed 99% COD and pigment in 4 hours.Such treatment effect is difficult to reach in a short period of time with biological treatment.The removal speed that this figure also illustrates pigment is fast than the removal speed of COD.
Shown pigment and the organic content of molasses containing waste water after step biological treatment (biodegradable fluid after the anaerobic digestion) and secondary treatment (sewage that discharge in the facultative oxidation pond) in the table 1 below.Data sheet light colour element and remaining organism can not be removed by biological treatment, color burn behind the anaerobic degradation, and also color is still very dark after oxidation pond is handled.Residual organic (TOC) can be thought unmanageable material, and its main component is a pigment.Biological degradation method only can be removed 50% to 60% organism, thereby the degradation capability that shows biological degradation method is low.
Table I
Molasses are produced the feature of the distillation waste water of alcohol
| Parameter | Numerical value | |||
| Unit | Slops | Waste water after the biological degradation | Oxidation pond waste water | |
| pH | 4.55 | 7.71 | 7.85 | |
| Color | Photoabsorption at 475nm | 18 | 30 | 28 |
| Organic content is represented with total organic carbon TOC | mg/L | 31,800 | 16,800 | 15,500 |
| Chlorine | mg/L | 3,786 | 3,308 | 4,646 |
| Total nitrogen | mg/L | 1,644 | 1,680 | 1,476 |
| Total phosphorus | mg/L | 131 | 141 | 60 |
| Specific conductivity | μS/cm | 15,000 | ||
Annotate: slops is the waste water after zymamsis and distillation are handled; Waste water after the biological degradation is the slops after anaerobic biological treatment; Oxidation pond waste water is by the slops after anaerobic degradation and the oxidation pond S biological treatment.
Example II, the electricity consumption oxidation style is removed the ammonia in the deep-well bittern
Under 5 volts of voltages and 3 amperes of conditions of actuating current, with sintering platinum system anode and titanium alloys cathodic electricity oxidation deep-well bittern.Table II has shown the feature of deep-well bittern.Under this electrolytic condition, between 30 minutes to 40 minutes, ammonia is thoroughly removed.The nitrite of low levels and nitrate show that ammonia may be converted to nitrogen.Fig. 9 has shown the variation that electrolytic process is removed the time course of ammonia.When ammonia was oxidized, total residual oxygenant (TRO) content was still very low.Exist as long as it should be noted that residual ammonia, the oxygenate content of hypochlorous acid (HClO) and hypobromous acid (HBrO) just remains on very low level.As long as there is ammonia to exist, just detect formation less than bromate (a kind of known carcinogenic substance).In any electrolysis treatment, all do not have the formation of bromic acid, can think the advantage of this treatment process.Therefore, when electrolytic process was purified waste water, the ammonia that appropriate dosage must be provided was for oxidation.Have now found that electrolytic process can effectively remove the ammonia (100ppm-200ppm) of high density from deep-well bittern.Therefore, treatment with electrolytic method can remove deammoniation quickly, and compares with the ozonize method with biological treatment, has more superiority.
Table II
The feature of deep-well bittern
| Parameter | Unit | Numerical value |
| pH | 7.0 | |
| Chlorine | mg/L | 17,300 |
| Bromine | mg/ | 100 |
| Iodine | mg/L | 12 |
| Ammonia nitrogen | mg/L | 140-240 |
| Chemical oxygen demand | mg/L | 45-55 |
| Supercarbonate | mg/L | 550-900 |
| Specific conductivity | μS/cm | 40,000-48,000 |
Example III, the electricity consumption oxidation style purifies the landfill waste leachate
In the tank (Fig. 3 and Fig. 4) of a reactor assembly (Fig. 1) or opening, the rubbish leachate of accumulating is carried out electrolysis treatment.Table III has shown that the rubbish drop goes out the feature of waste water.Figure 10 has shown that the time course of several indexs changes.In about 40 minutes, ammonia can be removed fully.Applied voltage also is 5 volts, and actuating current approximately is 2.8 amperes.And sintering platinum system anode and titanium alloys negative electrode have been used.After thoroughly removing deammoniation, organism (as COD) also is removed.And, studies have shown that the electrooxidation method also can be used for removing the ammonia and the COD of high density from sanitary landfill rubbish leachate.
Table III
The rubbish drop goes out the feature of waste water
| Parameter | Unit | Numerical value |
| pH | 7.5 | |
| Ammonia nitrogen | mg/L | 117 |
| Chemical oxygen demand | mg/L | 98 |
| Specific conductivity | μS/cm | 14,000-16,000 |
The floating example of electricity
Example I, electric floating method is removed the blue-green algae of excessive breeding
In the electric floating treating processes of blue-green algae, electrode will produce flocculation agent, as Al
+ 3Or Al (OH)
3(Al
+ 3And H
2The floss that the O alkaline reaction produces), make the algae particle form aggregation block or aggregation.The small bubble hydrogen that the negative electrode place produces is pooled in the algae aggregation block and as leafing agent the algae aggregation block is floated to fluid surface.Following Table IV has shown the feature of handling the lake water of preceding nutrition accumulation.Figure 11 has shown the principle of algae removal.The algae removal time course of Figure 12 changes demonstration, and this treatment process also can thoroughly be removed algae.Answer the floating method of electricity consumption can from the lake water of nutrition accumulation, remove prolific algae.Its efficient and treatment time are decided by to import the power or the actuating current of electricity.Handle the scale that necessary operations electric current (being the operation electric power indirectly) will depend on initial algae content and treatment system to a great extent.
Table IV
The feature of the lake water of nutrition accumulation
| Parameter | Unit | Numerical value |
| pH | 7.5 | |
| Chlorophyll | mg/m 3 | ＞200 |
| Total organic carbon | mg/L | 13 |
| Specific conductivity | μS/cm | 300-400 |
The inactive anode of electrochemical activity and the algae of anode (aluminum alloy anode) in the floating processing of unit that have throwing out and electric floating effect are simultaneously removed effect to be compared.The result shows that the algae maximum of independent floating effect is removed efficient and had only 50%, and algae all can not be removed.In order thoroughly to remove algae, use cohesion simultaneously and floating effect is vital.
As described, the present invention clearly can be changed to various ways.But these variations do not break away from thinking of the present invention and scope.All these variations all are included within the category of following claim.
Claims (7)
1. the method for an electrolysis treatment waste water, wherein electrolytic action is to be coupled to or integrated into an electrolytic module on the liquid circulation module by one to realize, electrolytic module is made up of a plurality of parallel negative electrode and the positive plate that link to each other with voltage source, wherein, the liquid circulation module comprises a cylindrical tubes with inlet end and exit end, this cylindrical tubes has also comprised one and has driven in liquid unit, and battery lead plate is enclosed in the cylindrical tubes of liquid circulation module and is fixed on the upstream section that drives in liquid unit; Treatment step comprises: the inlet end that waste water to be processed is incorporated into the liquid circulation module, then with the direction parallel electrolytic module of flowing through with battery lead plate, thereby by producing electric current to the electrode making alive, thereby discharge ion at anode and come oxidation or the floating pollutants in waste water of removing of electricity, thereby purify waste water, at last treated water is discharged from exit end.
2. the method for electrolysis treatment waste water according to claim 1, wherein the anode electrode plate of removing pollutent in the waste water by oxidation adopts agglomerating noble metal platinum, iridium, ruthenium, palladium or its alloy to make, and wherein adopts the polyvalent metal alloy of aluminium or iron by the floating anode electrode plate of removing pollutent in the waste water of electricity.
3. the method for electrolysis treatment waste water according to claim 1, wherein the cathode electrode plate of electrolytic module adopts the stainless steel or the titanium alloy that do not produce deposit in the electrolytic process to make.
4. according to the method for each the described electrolysis treatment waste water in the claim 1～3, wherein drive in liquid unit and comprise a squirt pump or density flow producer.
5. the method for electrolysis treatment waste water according to claim 1, wherein the pollutent object of Chu Liing comprises the algae of organism, ammonia nitrogen or excessive breeding.
6. a device comprises: one is coupled to or integrated into an electrolytic module on the liquid circulation module, electrolytic module is made up of a plurality of parallel negative electrode and the anode electrode plate that link to each other with voltage source, wherein, the liquid circulation module comprises a cylindrical tubes with inlet end and exit end, this cylindrical tubes has also comprised one and has driven in liquid unit, and battery lead plate is enclosed in the cylindrical tubes of liquid circulation module and is fixed on the upstream section that drives in liquid unit.
7. device according to claim 6, it is as wastewater treatment.
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| EP2149625B1 (en) * | 2007-05-11 | 2012-06-27 | M Hikari & Energy Laboratory Co., Ltd. | On-site integrated production plant |
| CN101805093A (en) * | 2010-03-10 | 2010-08-18 | 中国科学院生态环境研究中心 | Scale advanced treatment method for livestock and poultry farming waste water |
| CN103172144A (en) * | 2013-04-02 | 2013-06-26 | 湖南水木科技有限公司 | High-chemical-oxygen-demand (COD) oil-containing waste water treatment method and device |
| CN105000662A (en) * | 2015-06-30 | 2015-10-28 | 华南理工大学 | Method used for removing antibiotics in breeding industry wastewater via anaerobic self-electrolysis |
| CN105060648B (en) * | 2015-08-19 | 2017-05-31 | 福建省农业科学院科技干部培训中心 | Industrial circulating water fish culture denitrogenation Zero discharging system |
| EP3225597A1 (en) | 2016-03-29 | 2017-10-04 | Apria Systems, S.L. | Continuous water regeneration process in semi-closed circuits for the recirculating aquaculture industry and system for performing said process |
| CN105967404A (en) * | 2016-06-22 | 2016-09-28 | 安徽国能亿盛环保科技有限公司 | Industrial waste liquid treatment mechanism |
| CN105967303A (en) * | 2016-06-22 | 2016-09-28 | 安徽国能亿盛环保科技有限公司 | Environment-friendly device for neutralizing industrial waste liquid |
| CN105967403A (en) * | 2016-06-22 | 2016-09-28 | 安徽国能亿盛环保科技有限公司 | Chemical water purification device |
| CN105967423A (en) * | 2016-06-22 | 2016-09-28 | 安徽国能亿盛环保科技有限公司 | Wastewater chemical reaction treatment mechanism |
| CN106904696B (en) * | 2017-04-27 | 2023-03-31 | 中国葛洲坝集团第一工程有限公司 | Jet aeration electrochemical oxidation repair system for brackish black and odorous water body |
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| US4525254A (en) * | 1982-10-07 | 1985-06-25 | Gosudarstvenny Nauchno-Issledovatelsky I Proektny Institut Po Obogascheniju Rud Tsvetnykh Metallov "Kazmekhanobr" | Process and apparatus for purifying effluents and liquors |
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